EP2722370B1 - Photocatalytic coatings with fillers - Google Patents

Photocatalytic coatings with fillers Download PDF

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Publication number
EP2722370B1
EP2722370B1 EP12007180.8A EP12007180A EP2722370B1 EP 2722370 B1 EP2722370 B1 EP 2722370B1 EP 12007180 A EP12007180 A EP 12007180A EP 2722370 B1 EP2722370 B1 EP 2722370B1
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EP
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Prior art keywords
weight
coating material
baso
photocatalytically active
active agent
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EP12007180.8A
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German (de)
French (fr)
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EP2722370A1 (en
Inventor
Gerald Burgeth
Andreas Baindl
Marianne Burger
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Sto SE and Co KGaA
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Sto SE and Co KGaA
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Priority to EP12007180.8A priority Critical patent/EP2722370B1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C09D5/028—Pigments; Filters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1687—Use of special additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C08K2003/3054—Ammonium sulfates

Definitions

  • the present invention relates to photocatalytic coating materials.
  • the present invention relates to a coating material comprising at least one organic binder, at least one inorganic photocatalytically active agent and BaSO 4 as a functional filler.
  • the invention also relates to the use of such coating materials for the degradation of noxious gases contained in atmospheric air.
  • the invention relates to the use of BaSO 4 as a functional filler for increasing the activity of a photocatalytically active agent in a coating material.
  • Photocatalytic coatings of surfaces are coatings which contain a photocatalyst whose activity may affect certain properties of the coating.
  • coatings are used to produce a self-cleaning surface, or they serve to degrade harmful gases from the ambient air.
  • Photocatalytic coatings are known in the art.
  • this describes EP 1 735 372 a coating material with a binder and at least one particle having a size and / or surface roughness of 100 microns or less having filler and a photocatalytically active agent, wherein the binder is at least partially degraded by the photocatalytic action and a microstructured, self-cleaning surface is formed.
  • EP 1 753 831 describes coating materials with a binder and a photocatalyst of TiO 2 , which is surface-modified with carbon and or sulfur and is therefore photocatalytically active also with visible light.
  • the coating shows activity against microbial growth.
  • the German Utility Model DE 203 06 431 describes a photocatalyst-containing coating composition that is cementless and includes a calcium sulfate component.
  • the calcium sulfate is to be considered here as a binder component.
  • Such coatings are known as photocatalytic gypsum plasters, but can because of the low Weather resistance should not be used outdoors because CaSO 4 as the binder used for it has too little "binding force" and is too water-soluble.
  • silicate binders are contemplated. Silicate binders can not be further oxidized since Si is already in the oxidation state IV. However, since photocatalysis produces very nucleophilic and silicon-rich oxygen species (such as OH radicals or O 2- , etc.), the Si-O-Si bonds are attacked very quickly. There are nucleophilic substitution reactions and the silicate network is destroyed. The result is massive photocorrosion of the entire binder matrix. These processes are chemically comparable with alkaline digestion of silicates. To counteract this photocorrosion, manufacturers of such silicate coatings often simply use less TiO 2 than photocatalyst, with the result that the overall photocatalytic activity of these coatings is very poor.
  • the water glass binds very well to the TiO 2 , so that under certain circumstances, the TiO 2 catalyst particles coated and encapsulated. This leads to a further reduction of the photocatalytic activity.
  • Such coating of TiO 2 with silicates is also used selectively to "stabilize" pigmentary TiO 2 and so to reduce photocatalytic effectiveness. The undesired photocatalytic activity is suppressed by treatment with silicate.
  • cementitious coating materials can be considered.
  • Cement-bound coating compositions which are generally applied in thick layers, usually also show low photocatalytic activity, since usually very little of the expensive raw material TiO 2 is used. The largest part of the photocatalyst disappears in the depth of the coating and is lost for photocatalytic processes that occur only near the surface.
  • the continuous carbonation of cementitious coating compositions forms a near-surface CaCO 3 layer which adversely affects photocatalysis.
  • photocatalytic coatings when used to degrade noxious gases in the ambient air, should be so active that degradation of the noxious gases under the prevailing environmental conditions obeys First Order kinetics. This means that the transport of the noxious gas to the coating is the rate-limiting step and not the photocatalytic degradation reactions. However, this activity is typically not achieved by known systems.
  • the object of the present invention is to provide such coating material.
  • silicate binders are not sufficiently stable for providing photocatalytic coating materials.
  • a Persons skilled in the art of coating materials are aware of various silicate binders. Some examples are described above.
  • silicate binder may be called water glass or silica sol.
  • Silicate binders are not included in the coating materials of the present invention.
  • binder is to be understood as commonly used in the art.
  • a binder is in particular a curable, for example crosslinkable or condensable material which is present in liquid form before curing and which wets and binds solids contained in the composition or binds the composition to a substrate.
  • the binder forms a coherent matrix in the cured composition.
  • the term “filler” describes solids which increase the volume of the composition and which are already present as solids prior to curing of the binder. Filler particles are substantially isolated from each other in the cured composition and are enclosed by the binder matrix (optionally only partially). Conventional fillers typically do not significantly affect the properties of a composition.
  • the term “functional filler” refers to BaSO 4 which, as described in more detail below, has a significant impact on the photocatalytic activity of the photocatalytic agent contained in the coating material of the invention.
  • the inventors of the present invention have found that using BaSO 4 as a filler increases the photocatalytic efficiency of the coating material, without having to resort to substances which would render the coating composition unsuitable for outdoor use.
  • the amount of photocatalytic agent required in the coating material which is usually a high-priced material, can be reduced with otherwise equal efficiency, or the overall activity of the coating composition can be increased by the use of a low available filler, without resorting to other high-cost photocatalyst to have to fall back.
  • These coating materials are also suitable for outdoor use.
  • the coating materials according to the invention are suitable for the photocatalytic decomposition of noxious gases contained in atmospheric air, for example volatile organic compounds (VOC) or nitrogen oxides, such as NO and NO 2 .
  • VOC volatile organic compounds
  • the coating materials of the invention show a high activity even when using relatively small amounts of photocatalytically active agent. Therefore, the present invention also relates to Use of a coating material as defined above for degrading noxious gases contained in atmospheric air, in particular volatile organic compounds (VOC) or nitrogen oxides, such as NO or NO 2 .
  • organically bound coating materials which, in addition to a photocatalyst, also comprise BaSO 4 as a functional filler, have a high activity against noxious gases contained in ambient air and, in addition, are sufficiently weather-resistant for outdoor use.
  • the coating material according to the invention contains as binder an organic binder and can therefore be provided in a preferred embodiment substantially free of silicate binders. More preferably, the coating material of the invention is free of silicate binders.
  • the coating material according to the invention contains BaSO 4 .
  • barium sulfate is used as a filler, but in contrast to conventional fillers substantially changes the properties of the coating composition, namely the activity of the photocatalytically active agent contained increased compared to compositions containing a different filler instead of barium sulfate.
  • the inventors of the present invention have found that barium sulfate as a filler component exerts an excellent reinforcing effect on the activity of the photocatalytically active agent, particularly in the decomposition of noxious gases contained in ambient air.
  • Coating materials containing barium sulfate as a filler component also have excellent outdoor resistance due to the low water solubility of barium sulfate.
  • barium sulfate is particularly favorable available in comparison with conventional photocatalytically active agents. Therefore, when fillers containing barium sulfate are used, a coating material can be obtained be, which has a high photocatalytic activity, in particular against harmful gases contained in ambient air, and also low and very good outdoor resistance.
  • the barium sulfate can be present, for example, as natural barium sulfate, as synthetic barium sulfate or as a mixed filler containing more than 60% by weight, preferably more than 80% by weight, of BaSO 4 .
  • a mixed filler containing BaSO 4 may be a filler containing mixed crystals of BaSO 4 and another inorganic compound such as SrSO 4 , quartz or fluorite.
  • the mixed filler containing BaSO 4 has a low water solubility, in particular a water solubility of less than 0.1 g / l at 20 ° C.
  • the present invention relates to a coating material as defined herein, which is substantially free, preferably free of carbonaceous fillers, such as CaCO 3 .
  • the present inventors have found that the reinforcing effect BaSO 4 as a functional filler on the activity of the photocatalytically active agent is not linked to a high water solubility of the filler. Furthermore, the low water solubility of the functional filler contributes to the resistance of the coating material under outdoor conditions.
  • the inventors of the present invention have found that organically bound coatings containing barium sulfate in addition to a photocatalyst, such as TiO 2 , have a higher photocatalytic activity than coatings without BaSO 4 . This is astonishing at first, since BaSO 4 is present only as a solid next to the photocatalyst because of its poor solubility.
  • the functional filler of the present invention preferably has a particle size of at least 100 nm, more preferably at least 500 nm, even more preferably at least 1000 nm. Particle sizes below 100 nm show enhanced transparency, which is undesirable in the context of the present invention.
  • the functional filler of the present invention may have a particle size of less than 1 mm.
  • the coating material of the present invention may further contain other fillers which are not functional fillers in the sense of the present invention.
  • the prior art discloses a large number of such further fillers. Examples of it include aluminum hydroxide, sand, white pigment TiO 2 (rutile), and carbonaceous or siliceous fillers.
  • a compromise is usually chosen between the desired photocatalytic activity and the stability of the material.
  • the coating material is said to be durable over a normal renovation interval (typically about 10 to 20 years) but also to exhibit a satisfactory photocatalytic effect. Should the photocatalytic effect of a given composition be too low, it may be increased, such as by increasing the level of photocatalytic agent, by choosing a more active photocatalytic agent, etc. If the photocatalytic effect of a given composition is too high for durability over a typical renovation interval, this can be reduced, such as by choosing a more stable binder or stabilizing it with the aid of additives, by reducing the amount or activity of the photocatalytic agent, etc.
  • Organic binders suitable for coating materials are known in the art.
  • the binder serves to bond the solids contained in the coating material, such as the photocatalytically active agent contained and BaSO 4 as the functional filler, to each other or to the substrate on which the coating material is applied.
  • organic binders having sufficient photostability or the organic ones are selected Binders are stabilized by addition of suitable additives which influence the activity of the photocatalytically active agent. Such UV stabilizers are typically already added by the manufacturer.
  • the organic binder is selected from polymer dispersions, redispersants, polymers or copolymers.
  • the organic binder is selected from epoxy resins, alkyd resins, acrylic resins, melamine / formaldehyde resins, silicone resins, silanes, polysiloxanes, polyacrylates, polymethacrylates, polyvinyl compounds, polyurethanes, polyethers or polyesters, and copolymers or blends thereof.
  • the organic binder is selected from polymer dispersions containing acrylates, styrene acrylates, vinyl acetates, vinyl chlorides, and copolymers and copolymers thereof.
  • the organic binders may be one- or two-component binders, such as a binder of a crosslinkable polyacrylate and an aliphatic polyisocyanate.
  • the coating materials of the present invention may further contain an organic binder or a mixture of various organic binders.
  • photocatalytically active agents as used in the present invention are known in the art.
  • photocatalytically active agent is to be understood in this application a photocatalytically or photosensitizing substance acting under the influence of light oxygen and / or water can activate so that high oxidative oxygen species are formed or formed.
  • the photocatalytically active agent may be, for example, an inorganic photocatalytically active metal oxide or metal sulfide, preferably a metal oxide.
  • organic substances such as organometallic complex compounds can be used.
  • oxides or sulfides (more preferably oxides) of Ti, Zn, Fe, Mn, Mo and / or W preferably in a proportion of at least 60 wt.%, Particularly preferably at least 80 wt.%, In particular at least 90 wt.% , based on the total amount of the photocatalytically active agent.
  • the photocatalytically active agent is selected from zinc sulfide, zinc oxide and titanium oxide and mixtures thereof. Particularly preferred is the photocatalytically active agent TiO 2 (anatase).
  • photocatalytically active metal oxides or metal sulfides by coating.
  • the photocatalytically active agents of the present invention have no such deactivating coating.
  • a further adjustability of the catalytic properties and the degradation products produced can be achieved if the photocatalytically active agent at least one additive, in particular ion selected from C, N, S and / or of Pt, Rh, Mn, Cr, Ru, Ni, Pd , Fe, Co, Ir, Cu, Mo, Zr, Re, Ag and Au, in the form of their oxides and / or halides group, preferably in an amount of 40 wt.% Or less, particularly preferably 20 wt .-% or less, in particular 10 wt .-% or less, and more than 1 wt .-%, preferably more than 2.5 wt.%, In particular 5 wt.% or more, based on the total weight of the catalytically active agent having.
  • the photocatalytically active agent at least one additive, in particular ion selected from C, N, S and / or of Pt, Rh, Mn, Cr, Ru, Ni, Pd , Fe, Co, Ir, Cu
  • the treatment of a photocatalytically active agent with such an additive is also referred to as "doping".
  • This allows the catalytic property with wavelengths z. B. in the visible range of the solar spectrum, whereby the function of the coating on z. B. the sun facing north sides of a building is guaranteed.
  • For the degradation of organic materials usable photocatalysts are for example in the DE 197 57 496 A1 described. The disclosure of this document is hereby incorporated by reference into the specification in terms of the structure and composition of photocatalysts.
  • the photocatalytically active agent consists of titanium dioxide, in particular in amorphous and / or partially crystalline, rutile or anatase form, hydrates of titanium oxides and mixed forms thereof. Preferably, these are doped with C, N and / or S TiO 2 .
  • the coating material according to the invention comprises the organic binder or a mixture of several organic binders in an amount of 5% by weight to 50% by weight, based on the total solids content of the coating material.
  • the organic binder is contained in an amount of 7% by weight to 40% by weight, more preferably 10% by weight to 35% by weight.
  • the photocatalytically active agent is contained in an embodiment of the invention in an amount of from 2% by weight to 40% by weight, based on the total solids content of the coating material.
  • the photocatalytically active agent is contained in an amount of 3% by weight to 30% by weight, more preferably 5% by weight to 25% by weight, even more preferably 5% by weight to 10% by weight.
  • BaSO 4 as a functional filler is contained in an embodiment of the invention in an amount of from 2% by weight to 70% by weight, based on the total solids content of the coating material.
  • the content of BaSO 4 in the coating composition is greater than or equal to the content of photocatalytically active agent.
  • the functional filler is BaSO 4 in an amount of from 3 wt% to 60 wt%, preferably 5 wt% to 50 wt%, more preferably 5 wt% to 40 wt%.
  • the fillers contained in the coating material of the invention may consist entirely of BaSO 4 -containing functional filler as defined above.
  • conventional fillers which do not contain BaSO 4 are additionally used.
  • the upper limits of the functional filler content mentioned herein are preferably also to be understood as upper limits for the total filler content, ie the functional filler containing BaSO 4 is to a certain extent replaced by conventional filler.
  • the solid components of the coating material are usually dispersed in a liquid medium, e.g. Water in front.
  • a liquid medium e.g. Water in front.
  • the coating material according to the invention contains 10% by weight to 50% by weight of water before use.
  • the coating composition of the present invention may optionally contain, in addition to the above-mentioned essential ingredients (organic binder, photocatalytic agent and BaSO 4 ), further conventional additives, which are each known to a person skilled in the art. These additives include wetting and dispersing agents, thickeners, defoamers, film-forming aids, etc.
  • the content of BaSO 4 as a functional filler in the coating composition is greater than or equal to the content of the photocatalytically active agent.
  • the weight ratio of BaSO 4 to photocatalytically active agent is from 1: 1 to 10: 1, preferably 1.2: 1 to 5: 1.
  • the coating material of the present invention can be used in various applications.
  • the coating material may be present as a paint, in particular a facade paint, a paint, a glaze, a seal, a protective paint, a corrosion protection paint or a plaster.
  • the coating material of the present invention is particularly suitable for use outdoors, for example, for painting, painting, plastering or coating of building parts, such as concrete walls, brick walls or other walls, masonry, etc.
  • the coating material of the present invention is used outdoors.
  • the present invention also relates to the use of BaSO 4 as a functional filler as defined above for increasing the activity or efficiency of a photocatalytically active agent in a coating material, in particular with regard to the decomposition of noxious gases contained in ambient air.
  • Methanol was used as noxious gas. Methanol is relatively stable compared to other noxious gases. Therefore, an increased rate of degradation of methanol is also meaningful for other, less stable noxious gases.
  • the total volume of the system is 9.51.
  • the air is circulated in a closed circuit in a circle.
  • the FTIR spectrometer as detector absorbs complete spectra ranging from 4000 cm -1 to 700 cm -1 at given time intervals after addition of the pollutant. From these snapshots of the composition of the atmosphere in the system can be determined continuously and without delay, the concentration of the pollutant in the gas phase. Exposure is achieved with Philips TL 40W / 05 UV fluorescent tubes if UV photocurrent activity is to be determined, or Philips Master TL-D Super 80 36W / 840 conventional "Neonatal" tubes if the photocatalytic activity in the visible range of the light is to be determined. The exact intensities are given in the following embodiments and comparative examples.
  • the formulations according to Comparative Example 1 and Working Example 1 can be prepared by mixing the stated components in the stated amounts in a manner known per se.
  • the formulation of Comparative Example 1 and the formulation of Example 1 were each applied to aluminum foil and dried under normal room conditions. Before determining the photocatalytic activity, the samples were pre-exposed for 120 hours with an intensity of 10 W / m 2 UV-A. The samples were still moistened every 24 hours with distilled water and rinsed.
  • the photocatalytic degradation rate in Comparative Example 1 was 1.4 mg m -2 h -1 .
  • the photocatalytic degradation rate in Example 1 was 3.1 mg m -2 h -1 .
  • the increase in activity is clearly visible. More specifically, by replacing white pigment TiO 2 with BaSO 4, the photocatalytic activity more than doubles.
  • Component A is a compound having Component A:
  • Component B is a compound having Component B:
  • Components A and B are mixed in the ratio 100: 12 before use.
  • Component A is a compound having Component A:
  • Component B is a compound having Component B:
  • Components A and B are mixed in the ratio 100: 12 before use.
  • Component A of Comparative Example 2 and Exemplary Embodiment 2 can each be prepared by mixing the stated components in the stated amounts in a manner known per se. Component B is mixed before each application in the specified mixing ratio.
  • the formulation of Comparative Example 2 and the formulation of Example 2 were each applied to aluminum foil and dried under normal room conditions. Before determining the photocatalytic activity, the samples were pre-exposed for 120 hours with an intensity of 10 W / m 2 UV-A. The samples were still moistened every 24 hours with distilled water and rinsed.
  • the exposure was carried out with UV radiation with a total intensity of 17.0 W / m 2 in the wavelength range from 300 nm to 800 nm.
  • the UV-A content (315 nm-380 nm) was 6.7 W / m 2 .
  • the photocatalytic degradation rate in Comparative Example 2 was 16.2 mg m -2 h -1 .
  • the photocatalytic degradation rate in Example 2 was in contrast 20.3 mg m -2 h -1 .
  • An increase in activity is clearly visible.
  • Embodiment 2 differs of Comparative Example 2 only in that the filler CaCO 3 was replaced with the filler BaSO 4 .
  • the formulation according to embodiment 3 can be prepared by mixing the said components in the stated amounts in a manner known per se.
  • the plaster was applied to aluminum foil and dried under normal room conditions.
  • the sample was pre-exposed for 120 hours with an intensity of 10 W / m 2 UV-A.
  • the sample was moistened every 24 hours with distilled water and rinsed.
  • the exposure was carried out with UV radiation with a total intensity of 17.0 W / m 2 in the wavelength range of 300 nm to 800 nm.
  • the UV-A content (315 nm - 380 nm) was 6.7 W / m 2 .
  • the photocatalytic degradation rate was 6.1 mg m -2 h -1 . This is a remarkable activity particularly in view of the relatively low photocatalyst content.

Description

Die vorliegende Erfindung betrifft photokatalytische Beschichtungsmaterialien. Insbesondere betrifft die vorliegende Erfindung ein Beschichtungsmaterial, umfassend mindestens ein organisches Bindemittel, mindestens ein anorganisches photokatalytisch wirksames Mittel und BaSO4 als funktionellen Füllstoff. Die Erfindung betrifft auch die Verwendung derartiger Beschichtungsmaterialien zum Abbau von in Atmosphärenluft enthaltenen Schadgasen. Ferner betrifft die Erfindung die Verwendung von BaSO4 als funktionellem Füllstoff zur Steigerung der Aktivität eines photokatalytisch wirksamen Mittels in einem Beschichtungsmaterial.The present invention relates to photocatalytic coating materials. In particular, the present invention relates to a coating material comprising at least one organic binder, at least one inorganic photocatalytically active agent and BaSO 4 as a functional filler. The invention also relates to the use of such coating materials for the degradation of noxious gases contained in atmospheric air. Furthermore, the invention relates to the use of BaSO 4 as a functional filler for increasing the activity of a photocatalytically active agent in a coating material.

Hintergrund der ErfindungBackground of the invention

Photokatalytische Beschichtungen von Oberflächen, insbesondere von Aussenfassaden von Bauten, sind Beschichtungen, welche einen Photokatalysator enthalten, dessen Aktivität bestimmte Eigenschaften der Beschichtung beeinflussen kann. So werden derartige Beschichtungen zur Erzeugung einer selbstreinigenden Oberfläche verwendet, oder sie dienen dem Abbau von Schadgasen aus der Umgebungsluft.Photocatalytic coatings of surfaces, particularly exterior facades of buildings, are coatings which contain a photocatalyst whose activity may affect certain properties of the coating. Thus, such coatings are used to produce a self-cleaning surface, or they serve to degrade harmful gases from the ambient air.

Photokatalytische Beschichtungen sind im Stand der Technik bekannt. Beispielsweise beschreibt die EP 1 735 372 ein Beschichtungsmaterial mit einem Bindemittel und mindestens einem Teilchen mit einer Größe und/oder Oberflächenrauhigkeit von 100 µm oder weniger aufweisenden Füllstoff sowie einem photokatalytisch wirksamen Mittel, wobei das Bindemittel zumindest teilweise durch die photokatalytische Wirkung abgebaut wird und eine mikrostrukturierte, selbstreinigende Oberfläche entsteht.Photocatalytic coatings are known in the art. For example, this describes EP 1 735 372 a coating material with a binder and at least one particle having a size and / or surface roughness of 100 microns or less having filler and a photocatalytically active agent, wherein the binder is at least partially degraded by the photocatalytic action and a microstructured, self-cleaning surface is formed.

EP 1 753 831 beschreibt Beschichtungsmaterialien mit einem Bindemittel und einem Photokatalysator aus TiO2, das mit Kohlenstoff und oder Schwefel oberflächenmodifiziert ist und dadurch auch mit sichtbarem Licht photokatalytisch aktiv ist. Die Beschichtung zeigt Aktivität gegen mikrobiellen Bewuchs. EP 1 753 831 describes coating materials with a binder and a photocatalyst of TiO 2 , which is surface-modified with carbon and or sulfur and is therefore photocatalytically active also with visible light. The coating shows activity against microbial growth.

Die deutsche Gebrauchsmusterschrift DE 203 06 431 beschreibt eine Photokatalysator-haltige Beschichtungsmasse, die zementfrei ist und eine Calciumsulfat-Komponente beinhaltet. Das Calciumsulfat ist hier als Bindemittelbestandteil zu betrachten. Solche Beschichtungen sind als photokatalytische Gips-Putze bekannt, können jedoch wegen der niedrigen Witterungsbeständigkeit nicht im Außenbereich eingesetzt werden, da CaSO4 als das verwendete Bindemittel dafür zu wenig "Bindekraft" hat und zu stark wasserlöslich ist.The German Utility Model DE 203 06 431 describes a photocatalyst-containing coating composition that is cementless and includes a calcium sulfate component. The calcium sulfate is to be considered here as a binder component. Such coatings are known as photocatalytic gypsum plasters, but can because of the low Weather resistance should not be used outdoors because CaSO 4 as the binder used for it has too little "binding force" and is too water-soluble.

Im Stand der Technik ist allgemein das Vorurteil verbreitet, dass photokatalytische Beschichtungsmassen nicht organisch, auf Basis von Polymerdispersionen gebunden sein dürfen, sondern rein mineralisch, anorganisch - beispielsweise auf Basis von Wasserglas - gebunden sein müssen. Dieses Vorurteil ist oft in der Literatur zu finden, wie beispielsweise in Absatz [0007] der EP 1 809 707 B1 :

  • "Problematisch an der Verwendung photokatalytisch aktiver Pigmente, insbesondere des kostengünstigen Anatas in Beschichtungsmassen, welche organische Bindemittel enthalten, ist, dass das organische Bindemittel, in der Regel eine polymere Verbindung, durch die photokatalytischen Effekte angegriffen und dabei das organische Bindemittel abgebaut wird. Als Folge dieses Prozesses werden Pigment- und Füllstoffpartikel an der Oberfläche der Beschichtungsmasse freigelegt, was zum unerwünschten Phänomen der sogenannten Kreidung führt (siehe hierzu R. Benedix et al., Lacer No. 5, 2000, Seite 161 sowie R. Baumstark und M. Schwanz, Dispersionen für Bautenfarben, Acrylatsysteme in Theorie und Praxis, Seite 64, Curt R. Vincentz Verlag, Hannover, 2001 ). Auch ist bekannt, dass diese Beschichtungsmassen verstärkt zu Vergilbungsreaktionen neigen. Diese Effekte verhindern bislang den Einsatz organischer Bindemittel in diesem Arbeitsgebiet und erfordern die Verwendung von rein anorganischen Bindemitteln, wie beispielsweise Wasserglas, die keinem solchen Abbau unterliegen [siehe beispielsweise die japanische Patentanmeldung mit der Anmeldenummer 10-309419 (Nippon Paint Co. Ltd.)]."
In the prior art, the general prejudice is widespread that photocatalytic coating compositions must not be bound organically, based on polymer dispersions, but purely mineral, inorganic - for example, based on water glass - must be bound. This prejudice is often found in the literature, as for example in paragraph [0007] of EP 1 809 707 B1 :
  • "The problem with the use of photocatalytically active pigments, in particular the cost-effective anatase in coating compositions which contain organic binders, is that the organic binder, as a rule a polymeric compound, is attacked by the photocatalytic effects and the organic binder is degraded as a result In this process, pigment and filler particles are exposed on the surface of the coating composition, which leads to the undesirable phenomenon of so-called chalking (see R. Benedix et al., Lacer no. 5, 2000, page 161 such as R. Baumstark and M. Schwanz, Dispersions for Building Colors, Acrylate Systems in Theory and Practice, page 64, Curt R. Vincentz Verlag, Hannover, 2001 ). It is also known that these coating compositions are more prone to yellowing reactions. These effects hitherto prevent the use of organic binders in this field of work and require the use of purely inorganic binders, such as water glass, which are not subject to such degradation [see, for example, Japanese Patent Application No. 10-309419 (Nippon Paint Co. Ltd.)] . "

Als Alternative zu organischen Bindemitteln werden silikatische Bindemittel in Betracht gezogen. Silikatische Bindemittel können nicht weiter oxidiert werden, da sich Si bereits in der Oxidationsstufe IV befindet. Da jedoch bei der Photokatalyse sehr nukleophile und siliciumphile Sauerstoff-Spezies (wie OH-Radikale oder O2-, etc.) entstehen, werden die Si-O-Si-Bindungen sehr schnell angegriffen. Es kommt zu nukleophilen Substitutionsreaktionen, und das Silikat-Netzwerk wird zerstört. Die Folge ist eine massive Photokorrosion der gesamten Bindemittelmatrix. Chemisch zu vergleichen sind diese Vorgänge mit einem alkalischen Aufschluss von Silikaten. Um dieser Photokorrosion entgegen zu wirken, setzen die Hersteller solcher silikatischen Beschichtungsmassen oft einfach weniger TiO2 als Photokatalysator ein, mit der Folge, dass die photokatalytische Aktivität dieser Beschichtungen insgesamt sehr schlecht ist. Hinzu kommt, dass das Wasserglas noch sehr gut an das TiO2 bindet, so dass unter Umständen das TiO2-Katalysatorpartikel beschichtet und eingekapselt wird. Dies führt zu einer weiteren Minderung der photokatalytischen Aktivität. Ein derartiges Beschichten von TiO2 mit Silikaten wird auch gezielt eingesetzt, um pigmentäres TiO2 zu "stabilisieren" und so dessen photokatalytische Wirksamkeit zu vermindern. Die hier unerwünschte photokatalytische Aktivität wird durch das Behandeln mit Silikat unterdrückt.As an alternative to organic binders, silicate binders are contemplated. Silicate binders can not be further oxidized since Si is already in the oxidation state IV. However, since photocatalysis produces very nucleophilic and silicon-rich oxygen species (such as OH radicals or O 2- , etc.), the Si-O-Si bonds are attacked very quickly. There are nucleophilic substitution reactions and the silicate network is destroyed. The result is massive photocorrosion of the entire binder matrix. These processes are chemically comparable with alkaline digestion of silicates. To counteract this photocorrosion, manufacturers of such silicate coatings often simply use less TiO 2 than photocatalyst, with the result that the overall photocatalytic activity of these coatings is very poor. In addition, the water glass binds very well to the TiO 2 , so that under certain circumstances, the TiO 2 catalyst particles coated and encapsulated. This leads to a further reduction of the photocatalytic activity. Such coating of TiO 2 with silicates is also used selectively to "stabilize" pigmentary TiO 2 and so to reduce photocatalytic effectiveness. The undesired photocatalytic activity is suppressed by treatment with silicate.

Als weitere Alternative zu organischen Bindemittel kommen zementgebundene Beschichtungsmaterialien in Betracht. Zementgebundene Beschichtungsmassen, die in der Regel dickschichtig aufgebracht werden, zeigen üblicherweise ebenfalls geringe photokatalytische Aktivität, da meist nur sehr wenig des teuren Rohstoffs TiO2 eingesetzt wird. Der größte Anteil des Photokatalysators verschwindet in der Tiefe der Beschichtung und ist für photokatalytische Prozesse, die nur oberflächennah auftreten, verloren. Außerdem bildet sich durch die fortlaufende Carbonatisierung von zementösen Beschichtungsmassen eine oberflächennahe CaCO3-Schicht, die die Photokatalyse negativ beeinträchtigt.As a further alternative to organic binders, cementitious coating materials can be considered. Cement-bound coating compositions, which are generally applied in thick layers, usually also show low photocatalytic activity, since usually very little of the expensive raw material TiO 2 is used. The largest part of the photocatalyst disappears in the depth of the coating and is lost for photocatalytic processes that occur only near the surface. In addition, the continuous carbonation of cementitious coating compositions forms a near-surface CaCO 3 layer which adversely affects photocatalysis.

Generell sollten photokatalytische Beschichtungen, wenn sie zum Abbau von Schadgasen in der Umgebungsluft eingesetzt werden, derart aktiv sein, dass der Abbau der Schadgase unter den herrschenden Umweltbedingungen einer Kinetik Erster Ordnung gehorcht. Das bedeutet, dass der Transport des Schadgases an die Beschichtung der geschwindigkeitslimitierende Schritt ist und nicht die photokatalytischen Abbau-Reaktionen. Diese Aktivität wird jedoch von bekannten Systemen typischerweise nicht erreicht.Generally, photocatalytic coatings, when used to degrade noxious gases in the ambient air, should be so active that degradation of the noxious gases under the prevailing environmental conditions obeys First Order kinetics. This means that the transport of the noxious gas to the coating is the rate-limiting step and not the photocatalytic degradation reactions. However, this activity is typically not achieved by known systems.

Es besteht daher ein Bedarf an einem Beschichtungsmaterial, das einerseits gegen in der Umgebungsluft enthaltenen Schadgasen eine hohe Aktivität aufweist und andererseits für eine Verwendung im Außenbereich ausreichend witterungsbeständig und langlebig ist. Der vorliegenden Erfindung liegt die Aufgabe zugrunde ein, derartiges Beschichtungsmaterial bereitzustellen.There is therefore a need for a coating material which, on the one hand, has a high activity against noxious gases contained in the ambient air and, on the other hand, is sufficiently weather-resistant and long-lasting for outdoor use. The object of the present invention is to provide such coating material.

Zusammenfassung der ErfindungSummary of the invention

Die vorliegende Erfindung stellt ein Beschichtungsmaterial bereit, umfassend

  1. (a) mindestens ein organisches Bindemittel,
  2. (b) mindestens ein photokatalytisch wirksames Mittel und
  3. (c) BaSO4 als funktionellen Füllstoff,
wobei der Gehalt an BaSO4 in der Beschichtungsmasse größer oder gleich dem Gehalt an photokatalytisch wirksamen Mittel ist, und wobei das Beschichtungsmaterial vorzugsweise weitgehend frei, stärker bevorzugt frei von silikatischen Bindemitteln ist.The present invention provides a coating material comprising
  1. (a) at least one organic binder,
  2. (B) at least one photocatalytically active agent and
  3. (c) BaSO 4 as a functional filler,
wherein the content of BaSO 4 in the coating composition is greater than or equal to the content of photocatalytically active agent, and wherein the coating material is preferably substantially free, more preferably free of silicate binders.

Die Erfinder der vorliegenden Erfindung haben entgegen der vorstehend beschriebenen Vorurteile im Stand der Technik gefunden, dass silikatische Bindemittel nicht ausreichend stabil sind für die Bereitstellung von photokatalytisch wirksamen Beschichtungsmaterialien. Einem Fachmann auf dem Gebiet von Beschichtungsmaterialien sind verschiedene silikatische Bindemittel bekannt. Einige Beispiele dafür sind vorstehend beschrieben. Insbesondere können als Beispiele für solche erfindungsgemäß ungeeignete silikatische Bindemittel können Wasserglas oder Kieselsol genannt werden. In den Beschichtungsmaterialien der vorliegenden Erfindung sind silikatische Bindemittel nicht enthalten.The inventors of the present invention have found, contrary to the prior art prejudices described above, that silicate binders are not sufficiently stable for providing photocatalytic coating materials. a Persons skilled in the art of coating materials are aware of various silicate binders. Some examples are described above. In particular, as examples of such unsuitable according to the invention silicate binder may be called water glass or silica sol. Silicate binders are not included in the coating materials of the present invention.

Der Begriff "Bindemittel" ist hierbei wie üblicherweise im Fachgebiet verwendet zu verstehen. Ein Bindemittel ist insbesondere ein aushärtbares, z.B. vernetzbares oder kondensierbares Material, dass vor dem Aushärten in flüssiger Form vorliegt und welches in der Zusammensetzung enthaltene Feststoffe benetzt und aneinander bindet bzw. die Zusammensetzung an eine Unterlage bindet. Das Bindemittel bildet in der ausgehärteten Zusammensetzung eine zusammenhängende Matrix. Im Gegensatz dazu beschreibt der Begriff "Füllstoff" Feststoffe, welche das Volumen der Zusammensetzung erhöhen und die bereits vor dem aushärten des Bindemittels als Feststoffe vorliegen. Füllstoffteilchen liegen in der ausgehärteten Zusammensetzung im Wesentlichen voneinander isoliert vor und werden von der Bindemittelmatrix (gegebenenfalls nur teilweise) umschlossen. Herkömmliche Füllstoffe beeinflussen üblicherweise die Eigenschaften einer Zusammensetzung nicht wesentlich. Im Gegensatz dazu bezieht sich der Begriff "funktioneller Füllstoff" wie hierin verwendet auf BaSO4, welches wie nachstehend detaillierter beschrieben einen wesentlichen Einfluss auf die photokatalytische Aktivität des in dem erfindungsgemäßen Beschichtungsmaterial enthaltenen photokatalytisch wirksamen Mittels zeigt.The term "binder" is to be understood as commonly used in the art. A binder is in particular a curable, for example crosslinkable or condensable material which is present in liquid form before curing and which wets and binds solids contained in the composition or binds the composition to a substrate. The binder forms a coherent matrix in the cured composition. In contrast, the term "filler" describes solids which increase the volume of the composition and which are already present as solids prior to curing of the binder. Filler particles are substantially isolated from each other in the cured composition and are enclosed by the binder matrix (optionally only partially). Conventional fillers typically do not significantly affect the properties of a composition. In contrast, as used herein, the term "functional filler" refers to BaSO 4 which, as described in more detail below, has a significant impact on the photocatalytic activity of the photocatalytic agent contained in the coating material of the invention.

Die Erfinder der vorliegenden Erfindung haben gefunden, dass mit Hilfe von BaSO4 als Füllstoff die Aktivität des photokatalytisch wirksamen Mittels bzw. photokatalytische Effizienz des Beschichtungsmaterials gesteigert, ohne dabei auf Substanzen zurückgreifen zu müssen, die die Beschichtungszusammensetzung für den Einsatz im Außenbereich ungeeignet machen würden. Somit kann die Menge des in dem Beschichtungsmaterial erforderlichen photokatalytisch wirksamen Mittels, welches in der Regel ein hochpreisiges Material ist, bei sonst gleicher Wirksamkeit reduziert werden, oder die Gesamtaktivität der Beschichtungszusammensetzung kann durch die Verwendung eines günstig erhältlichen Füllstoffs gesteigert werden, ohne auf weiteren hochpreisigen Photokatalysator zurückgreifen zu müssen. Diese Beschichtungsmaterialien sind ferner für den Außeneinsatz geeignet.The inventors of the present invention have found that using BaSO 4 as a filler increases the photocatalytic efficiency of the coating material, without having to resort to substances which would render the coating composition unsuitable for outdoor use. Thus, the amount of photocatalytic agent required in the coating material, which is usually a high-priced material, can be reduced with otherwise equal efficiency, or the overall activity of the coating composition can be increased by the use of a low available filler, without resorting to other high-cost photocatalyst to have to fall back. These coating materials are also suitable for outdoor use.

Die erfindungsgemäßen Beschichtungsmaterialien sind geeignet zum photokatalytischen Abbau von in Atmosphärenluft enthaltenen Schadgasen, z.B. volatilen organischen Verbindungen (VOC) oder Stickoxiden, wie etwa NO und NO2. Dabei zeigen die Beschichtungsmaterialien der Erfindung eine hohe Aktivität selbst bei Verwendung relativ geringer Mengen an photokatalytisch wirksamem Mittel. Daher betrifft die vorliegende Erfindung auch die Verwendung eines Beschichtungsmaterials wie vorstehend definiert zum Abbau von in Atmosphärenluft enthaltenen Schadgasen, insbesondere volatilen organischen Verbindungen (VOC) oder Stickoxiden, wie etwas NO oder NO2.The coating materials according to the invention are suitable for the photocatalytic decomposition of noxious gases contained in atmospheric air, for example volatile organic compounds (VOC) or nitrogen oxides, such as NO and NO 2 . In this case, the coating materials of the invention show a high activity even when using relatively small amounts of photocatalytically active agent. Therefore, the present invention also relates to Use of a coating material as defined above for degrading noxious gases contained in atmospheric air, in particular volatile organic compounds (VOC) or nitrogen oxides, such as NO or NO 2 .

Die Erfinder der vorliegenden Erfindung haben gefunden, dass organisch gebundene Beschichtungsmaterialien, die neben einem Photokatalysator auch BaSO4 als funktionellen Füllstoff umfassen, eine hohe Wirkung gegen in Umgebungsluft enthaltene Schadgase zeigen und zudem für einen Einsatz im Außenbereich ausreichend witterungsbeständig sind.The inventors of the present invention have found that organically bound coating materials which, in addition to a photocatalyst, also comprise BaSO 4 as a functional filler, have a high activity against noxious gases contained in ambient air and, in addition, are sufficiently weather-resistant for outdoor use.

Weitere Ausführungsformen der Erfindung sind in der folgenden Beschreibung und den angefügten Ansprüchen beschrieben.Further embodiments of the invention are described in the following description and the appended claims.

Detaillierte Beschreibung der ErfindungDetailed description of the invention

Die vorliegende Erfindung stellt ein Beschichtungsmaterial bereit, umfassend

  1. (a) mindestens ein organisches Bindemittel,
  2. (b) mindestens ein photokatalytisch wirksames Mittel und
  3. (c) BaSO4 als funktionellem Füllstoff, wobei der Gehalt an BaSO4 in der Beschichtungsmasse größer oder gleich dem Gehalt an photokatalytisch wirksamen Mittel ist.
The present invention provides a coating material comprising
  1. (a) at least one organic binder,
  2. (B) at least one photocatalytically active agent and
  3. (c) BaSO 4 as a functional filler, wherein the content of BaSO 4 in the coating composition is greater than or equal to the content of photocatalytically active agent.

Das erfindungsgemäße Beschichtungsmaterial enthält als Bindemittel ein organisches Bindemittel und kann daher in einer bevorzugten Ausführungsform weitgehend frei von silikatischen Bindemitteln bereitgestellt werden. Stärker bevorzugt ist das Beschichtungsmaterial der Erfindung frei von silikatischen Bindemitteln.The coating material according to the invention contains as binder an organic binder and can therefore be provided in a preferred embodiment substantially free of silicate binders. More preferably, the coating material of the invention is free of silicate binders.

Wie vorstehend ausgeführt enthält das erfindungsgemäße Beschichtungsmaterial BaSO4. Dabei wird Bariumsulfat als ein Füllstoff eingesetzt, der jedoch im Gegensatz zu herkömmlichen Füllstoffen die Eigenschaften der Beschichtungszusammensetzung wesentlich verändert, nämlich die Aktivität des enthaltenen photokatalytisch wirksamen Mittels erhöht, im Vergleich zu Zusammensetzungen, die anstelle von Bariumsulfat einen anderen Füllstoff enthalten. Die Erfinder der vorliegenden Erfindung haben gefunden, das Bariumsulfat als Füllstoffbestandteil eine hervorragende Verstärkungswirkung auf die Aktivität des photokatalytisch wirksamen Mittels, insbesondere bei der Zersetzung von in Umgebungsluft enthaltenen Schadgasen ausübt. Beschichtungsmaterialien, die Bariumsulfat als Füllstoffbestandteil enthalten, weisen zudem aufgrund der geringen Wasserlöslichkeit von Bariumsulfat eine hervorragende Außenbeständigkeit auf. Ferner ist Bariumsulfat insbesondere im Vergleich mit üblichen photokatalytisch wirksamen Mitteln ausgesprochen günstig erhältlich. Daher kann bei Verwendung von Füllstoffen, die Bariumsulfat erhalten, ein Beschichtungsmaterial erhalten werden, das eine hohe photokatalytische Aktivität, insbesondere gegen in Umgebungsluft enthaltenen Schadgasen aufweist, und zudem günstig und sehr gut außenbeständig ist.As stated above, the coating material according to the invention contains BaSO 4 . In this case, barium sulfate is used as a filler, but in contrast to conventional fillers substantially changes the properties of the coating composition, namely the activity of the photocatalytically active agent contained increased compared to compositions containing a different filler instead of barium sulfate. The inventors of the present invention have found that barium sulfate as a filler component exerts an excellent reinforcing effect on the activity of the photocatalytically active agent, particularly in the decomposition of noxious gases contained in ambient air. Coating materials containing barium sulfate as a filler component also have excellent outdoor resistance due to the low water solubility of barium sulfate. Furthermore, barium sulfate is particularly favorable available in comparison with conventional photocatalytically active agents. Therefore, when fillers containing barium sulfate are used, a coating material can be obtained be, which has a high photocatalytic activity, in particular against harmful gases contained in ambient air, and also low and very good outdoor resistance.

Das Bariumsulfat kann beispielsweise als natürliches Bariumsulfat, als synthetisches Bariumsulfat oder als Mischfüllstoff, enthaltend mehr als 60 Gew.%, vorzugsweise mehr als 80 Gew.% BaSO4, vorliegen. Ein BaSO4 enthaltender Mischfüllstoff kann besielsweise ein Füllstoff sein, enthaltend Mischkristalle aus BaSO4 und einer anderen anorganischen Verbindung, wie etwa SrSO4, Quarz oder Fluorit.The barium sulfate can be present, for example, as natural barium sulfate, as synthetic barium sulfate or as a mixed filler containing more than 60% by weight, preferably more than 80% by weight, of BaSO 4 . By way of example, a mixed filler containing BaSO 4 may be a filler containing mixed crystals of BaSO 4 and another inorganic compound such as SrSO 4 , quartz or fluorite.

Der BaSO4 enthaltende Mischfüllstoff weist in einer bevorzugten Ausführungsform eine geringe Wasserlöslichkeit auf, insbesondere eine Wasserlöslichkeit von weniger als 0,1 g/l bei 20°C.In a preferred embodiment, the mixed filler containing BaSO 4 has a low water solubility, in particular a water solubility of less than 0.1 g / l at 20 ° C.

In einer weiteren Ausführungsform betrifft die vorliegende Erfindung ein Beschichtungsmaterial wie hierin definiert, welches weitgehend frei, vorzugsweise frei von carbonatischen Füllstoffen, wie etwa CaCO3, ist.In a further embodiment, the present invention relates to a coating material as defined herein, which is substantially free, preferably free of carbonaceous fillers, such as CaCO 3 .

Die vorliegenden Erfinder haben festgestellt, dass die verstärkende Wirkung BaSO4 als funktionellem Füllstoff auf die Aktivität des photokatalytisch wirksamen Mittels nicht an eine hohe Wasserlöslichkeit des Füllstoffs gebunden ist. Ferner trägt die geringe Wasserlöslichkeit des funktionellen Füllstoffs zur Beständigkeit des Beschichtungsmaterials unter Außenbedingungen bei.The present inventors have found that the reinforcing effect BaSO 4 as a functional filler on the activity of the photocatalytically active agent is not linked to a high water solubility of the filler. Furthermore, the low water solubility of the functional filler contributes to the resistance of the coating material under outdoor conditions.

Die Erfinder der vorliegenden Erfindung haben festgestellt, dass organisch gebundene Beschichtungen, die neben einem Photokatalysator, wie etwa TiO2, auch Bariumsulfat enthalten, eine höhere photokatalytische Aktivität aufwiesen als Beschichtungen ohne BaSO4. Dies ist zunächst äußerst erstaunlich, da BaSO4 aufgrund seiner Schwerlöslichkeit nur als Feststoff neben dem Photokatalysator vorliegt.The inventors of the present invention have found that organically bound coatings containing barium sulfate in addition to a photocatalyst, such as TiO 2 , have a higher photocatalytic activity than coatings without BaSO 4 . This is astonishing at first, since BaSO 4 is present only as a solid next to the photocatalyst because of its poor solubility.

Der funktionelle Füllstoff der vorliegenden Erfindung weist vorzugsweise eine Teilchengröße von mindestens 100nm, stärker bevorzugt mindestens 500nm, noch stärker bevorzugt mindestens 1000nm auf. Teilchengrößen unterhalb von 100nm zeigen eine verstärkte Transparenz, was im Zusammenhang mit der vorliegenden Erfindung unerwünscht ist. Der funktionelle Füllstoff der vorliegenden Erfindung kann eine Teilchengröße von weniger als 1 mm aufweisen.The functional filler of the present invention preferably has a particle size of at least 100 nm, more preferably at least 500 nm, even more preferably at least 1000 nm. Particle sizes below 100 nm show enhanced transparency, which is undesirable in the context of the present invention. The functional filler of the present invention may have a particle size of less than 1 mm.

Das Beschichtungsmaterial der vorliegenden Erfindung kann darüber hinaus auch weitere Füllstoffe enthalten, die kein funktioneller Füllstoff in Sinne der vorliegenden Erfindung sind. Im Stand der Technik ist eine Vielzahl solcher weiteren Füllstoffe bekannt. Beispiele davon schließen Aluminiumhydroxid, Sand, Weißpigment TiO2 (Rutil), und carbonatische oder silikatische Füllstoffe ein.The coating material of the present invention may further contain other fillers which are not functional fillers in the sense of the present invention. The prior art discloses a large number of such further fillers. Examples of it include aluminum hydroxide, sand, white pigment TiO 2 (rutile), and carbonaceous or siliceous fillers.

Das Beschichtungsmaterial der vorliegenden Erfindung enthält ferner als wesentlichen Bestandteil ein organisches Bindemittel. Die Witterungsbeständigkeit des erfindungsgemäßen Beschichtungsmaterials wird durch die Verwendung eines organischen Bindemittels sichergestellt. Ferner weisen organische Bindemittel im Gegensatz zu silikatischen Bindemittel eine relativ hohe photokatalytische Stabilität auf. Organische photokatalysatorhaltige Bindemittelsysteme neigen zwar aufgrund des oxidativen Abbaus der Bindemittelmatrix zu einer gewissen Kreidung, doch kann diese Kreidung gezielt gesteuert und damit ausreichend kontrolliert werden, beispielsweise durch

  • die Photostabilität des Bindemittels selbst, d.h. die Auswahl eines organischen Bindemittels mit besonders geringer photochemischer Zersetzbarkeit
  • die Aktivität und Menge des Photokatalysators
  • Additive, die die Aktivität des Photokatalysator beeinflussen, wie etwa Fluor oder Phosphor haltige Hydrophobierungsmittel
  • die "Verdünnung" des Photokatalysatorgehalts durch andere Füllstoffe, die photokatalytisch nicht aktiv sind.
The coating material of the present invention further contains as an essential ingredient an organic binder. The weather resistance of the coating material according to the invention is ensured by the use of an organic binder. Furthermore, unlike silicate binders, organic binders have a relatively high photocatalytic stability. Although organic photocatalyst-containing binder systems tend due to the oxidative degradation of the binder matrix to a certain chalking, but this chalking can be selectively controlled and thus controlled sufficiently, for example by
  • the photostability of the binder itself, ie the selection of an organic binder with particularly low photochemical decomposability
  • the activity and amount of the photocatalyst
  • Additives that affect the activity of the photocatalyst, such as fluorine or phosphorus-containing hydrophobing agents
  • the "dilution" of the photocatalyst content by other fillers that are not photocatalytically active.

Bei der Bereitstellung eines erfindungsgemäßen Beschichtungsmaterials wird daher üblicherweise ein Kompromiss zwischen der gewünschten photokatalytischen Aktivität und der Stabilität des Materials gewählt. Das Beschichtungsmaterial soll über ein normales Renovierungsintervall (typischerweise etwa 10 bis 20 Jahre) beständig sein aber auch eine zufriedenstellende photokatalytische Wirkung zeigen. Sollte die photokatalytische Wirkung einer gegebenen Zusammensetzung zu gering sein so kann diese gesteigert werden, etwa durch dir Erhöhung des Gehalts an photokatalytisch wirksamen Mittel, durch die Wahl eines aktiveren photokatalytischen Mittel, etc. Wenn die photokatalytische Wirkung einer gegebenen Zusammensetzung zu hoch ist um die Beständigkeit über ein typisches Renovierungsintervall zu gewährleisten so kann diese verringert werden, etwa indem ein stabileres Bindemittel gewählt wird oder dieses mit Hilfe von Additiven stabilisiert wird, indem die Menge oder Aktivität des photokatalytischen Mittel verringert wird, etc.In providing a coating material according to the invention, therefore, a compromise is usually chosen between the desired photocatalytic activity and the stability of the material. The coating material is said to be durable over a normal renovation interval (typically about 10 to 20 years) but also to exhibit a satisfactory photocatalytic effect. Should the photocatalytic effect of a given composition be too low, it may be increased, such as by increasing the level of photocatalytic agent, by choosing a more active photocatalytic agent, etc. If the photocatalytic effect of a given composition is too high for durability over a typical renovation interval, this can be reduced, such as by choosing a more stable binder or stabilizing it with the aid of additives, by reducing the amount or activity of the photocatalytic agent, etc.

Organische Bindemittel, die für Beschichtungsmaterialien geeignet sind, sind im Stand der Technik bekannt. Das Bindemittel dient dazu, die im Beschichtungsmaterial enthaltenen Feststoffe, wie etwas das enthaltene photokatalytisch wirksame Mittel und BaSO4 als den funktionellen Füllstoff, miteinander bzw. mit der Unterlage, auf der das Beschichtungsmaterial aufgebracht wird, zu verbinden. Gemäß der vorliegenden Erfindung werden organische Bindemittel gewählt, die eine ausreichende Photostabilität aufweisen, oder die organischen Bindemittel werden durch Zusatz geeigneter Additive, die die Aktivität des photokatalytisch wirksamen Mittels beeinflussen, stabilisiert. Derartige UV-Stabilisatoren werden typischerweise bereits von Herstellerseite zugesetzt.Organic binders suitable for coating materials are known in the art. The binder serves to bond the solids contained in the coating material, such as the photocatalytically active agent contained and BaSO 4 as the functional filler, to each other or to the substrate on which the coating material is applied. According to the present invention, organic binders having sufficient photostability or the organic ones are selected Binders are stabilized by addition of suitable additives which influence the activity of the photocatalytically active agent. Such UV stabilizers are typically already added by the manufacturer.

In einer Ausführungsform ist das organische Bindemittel ausgewählt aus Polymerdispersionen, Redispergiermitteln, Polymerisaten oder Mischpolymerisaten. In einer stärker bevorzugten Ausführungsform ist das organische Bindemittel ausgewählt aus Epoxidharzen, Alkydharzen, Acrylharzen, Melamin/Formaldehyd-Harzen, Silikonharzen, Silanen, Polysiloxanen, Polyacrylaten, Polymethacrylaten, Polyvinylverbindungenn, Polyurethanen, Polyethern oder Polyestern und Copolymeren oder Mischungen davon. In einer noch stärker bevorzugten Ausführungsform ist das organische Bindemittel ausgewählt aus Polymerdispersionen, enthaltend Acrylate, Styrolacrylate, Vinylacetate, Vinychloride sowie Misch- und Co-Polymere davon. Die organischen Bindemittel können ein oder zweikomponentige Bindemittel, etwa ein Bindemittel aus einem vernetzbaren Polyacrylat und einem aliphatischen Polyisocyanat, sein. Die Beschichtungsmaterialien der vorliegenden Erfindung können ferner ein organisches Bindemittel oder eine Gemisch von verschiedenen organischen Bindemitteln enthalten.In one embodiment, the organic binder is selected from polymer dispersions, redispersants, polymers or copolymers. In a more preferred embodiment, the organic binder is selected from epoxy resins, alkyd resins, acrylic resins, melamine / formaldehyde resins, silicone resins, silanes, polysiloxanes, polyacrylates, polymethacrylates, polyvinyl compounds, polyurethanes, polyethers or polyesters, and copolymers or blends thereof. In an even more preferred embodiment, the organic binder is selected from polymer dispersions containing acrylates, styrene acrylates, vinyl acetates, vinyl chlorides, and copolymers and copolymers thereof. The organic binders may be one- or two-component binders, such as a binder of a crosslinkable polyacrylate and an aliphatic polyisocyanate. The coating materials of the present invention may further contain an organic binder or a mixture of various organic binders.

Ein weiterer wesentlicher Bestandteil des Beschichtungsmaterials der vorliegenden Erfindung ist ein photokatalytisch wirksames Mittel. Photokatalytisch wirksame Mittel, wie sie in der vorliegenden Erfindung Verwendung finden, sind im Stand der Technik bekannt. Unter photokatalytisch wirksames Mittel ist in dieser Anmeldung eine photokatalytisch oder photosensibilisierend agierende Substanz zu verstehen, die unter Lichteinfluss Sauerstoff und/oder Wasser derart aktivieren kann, so dass hoch oxidative Sauerstoff-Spezies entstehen oder gebildet werden.Another essential ingredient of the coating material of the present invention is a photocatalytically active agent. Photocatalytically active agents as used in the present invention are known in the art. By photocatalytically active agent is to be understood in this application a photocatalytically or photosensitizing substance acting under the influence of light oxygen and / or water can activate so that high oxidative oxygen species are formed or formed.

Das photokatalytisch wirksame Mittel kann beispielsweise ein anorganisches photokatalytisch wirksames Metalloxid oder Metallsulfid, vorzugsweise ein Metalloxid sein. Neben den erwähnten (anorganischen) Metalloxiden und -sulfiden, können auch organische Substanzen wie beispielsweise metallorganische Komplexverbindungen eingesetzt werden. Bevorzugt sind Oxide oder Sulfide (stärker bevorzugt Oxide) von Ti, Zn, Fe, Mn, Mo und/oder W, vorzugsweise mit einem Anteil von mindestens 60 Gew.%, besonders bevorzugt mindestens 80 Gew.%, insbesondere mindestens 90 Gew.%, bezogen auf die Gesamtmenge des photokatalytisch wirksamen Mittels. In einer bevorzugten Ausführungsform ist das photokatalytisch wirksame Mittel ausgewählt aus Zinksulfid, Zinkoxid und Titanoxid und Mischungen davon. Besonders bevorzugt ist das photokatalytisch wirksame Mittel TiO2 (Anatas).The photocatalytically active agent may be, for example, an inorganic photocatalytically active metal oxide or metal sulfide, preferably a metal oxide. In addition to the mentioned (inorganic) metal oxides and sulfides, organic substances such as organometallic complex compounds can be used. Preferred are oxides or sulfides (more preferably oxides) of Ti, Zn, Fe, Mn, Mo and / or W, preferably in a proportion of at least 60 wt.%, Particularly preferably at least 80 wt.%, In particular at least 90 wt.% , based on the total amount of the photocatalytically active agent. In a preferred embodiment, the photocatalytically active agent is selected from zinc sulfide, zinc oxide and titanium oxide and mixtures thereof. Particularly preferred is the photocatalytically active agent TiO 2 (anatase).

Es ist in Stand der Technik bekannt photokatalytisch wirksame Metalloxide oder Metallsulfide durch beschichten zu deaktivieren. Die photokatalytisch wirksamen Mittel der vorliegenden Erfindung weisen keine derartige deaktivierende Beschichtung auf.It is known in the art to deactivate photocatalytically active metal oxides or metal sulfides by coating. The photocatalytically active agents of the present invention have no such deactivating coating.

Eine weitere Einstellbarkeit der katalytischen Eigenschaften und der erzeugten Abbauprodukte ist erreichbar, wenn das photokatalytisch wirksame Mittel mindestens ein Additiv, insbesondere Ion, ausgewählt aus C, N, S und/oder der aus Pt, Rh, Mn, Cr, Ru, Ni, Pd, Fe, Co, Ir, Cu, Mo, Zr, Re, Ag und Au, in Form ihrer Oxide und/oder Halogenide bestehenden Gruppe, vorzugsweise mit einem Anteil von 40 Gew. % oder weniger, besonders bevorzugt 20 Gew.-% oder weniger, insbesondere 10 Gew.-% oder weniger, und mehr als 1 Gew.-%, vorzugsweise mehr als 2,5 Gew. %, insbesondere 5 Gew. % oder mehr, bezogen auf das Gesamtgewicht des katalytisch wirksamen Mittels, aufweist. Die Behandlung eine photokatalytisch wirksamen Mittels mit einem derartigen Additiv wird auch als "Dotierung" bezeichnet. Dadurch lässt sich die katalytische Eigenschaft auch mit Wellenlängen z. B. im sichtbaren Bereich des solaren Spektrums anregen, wodurch die Funktion der Beschichtung auch auf z. B. der Sonne abgewandten Nordseiten eines Gebäudes gewährleistet ist. Zum Abbau organischer Materialien einsetzbare Photokatalysatoren sind beispielsweise in der DE 197 57 496 A1 beschrieben. Der Offenbarungsgehalt dieser Schrift wird hinsichtlich des Aufbaus und der Zusammensetzung von Photokatalysatoren hiermit durch ausdrückliche Inbezugnahme in diese Beschreibung aufgenommen.A further adjustability of the catalytic properties and the degradation products produced can be achieved if the photocatalytically active agent at least one additive, in particular ion selected from C, N, S and / or of Pt, Rh, Mn, Cr, Ru, Ni, Pd , Fe, Co, Ir, Cu, Mo, Zr, Re, Ag and Au, in the form of their oxides and / or halides group, preferably in an amount of 40 wt.% Or less, particularly preferably 20 wt .-% or less, in particular 10 wt .-% or less, and more than 1 wt .-%, preferably more than 2.5 wt.%, In particular 5 wt.% or more, based on the total weight of the catalytically active agent having. The treatment of a photocatalytically active agent with such an additive is also referred to as "doping". This allows the catalytic property with wavelengths z. B. in the visible range of the solar spectrum, whereby the function of the coating on z. B. the sun facing north sides of a building is guaranteed. For the degradation of organic materials usable photocatalysts are for example in the DE 197 57 496 A1 described. The disclosure of this document is hereby incorporated by reference into the specification in terms of the structure and composition of photocatalysts.

In einer bevorzugten Ausführungsform besteht das photokatalytisch wirksame Mittel aus Titandioxid, insbesondere in amorpher und/oder teilkristalliner, Rutil- oder Anatasform, Hydraten von Titanoxiden sowie Mischformen daraus. Vorzugsweise handelt es sich dabei um mit C, N und/oder S dotiertes TiO2.In a preferred embodiment, the photocatalytically active agent consists of titanium dioxide, in particular in amorphous and / or partially crystalline, rutile or anatase form, hydrates of titanium oxides and mixed forms thereof. Preferably, these are doped with C, N and / or S TiO 2 .

Das erfindungsgemäße Beschichtungsmaterial enthält in einer Ausführungsform das organische Bindemittel oder ein Gemisch von mehreren organischen Bindemitteln in einer Menge von 5 Gew.% bis 50 Gew.%, bezogen auf den Gesamtfeststoffgehalt des Beschichtungsmaterials. Vorzugsweise ist das organische Bindemittel in einer Menge von 7 Gew.% bis 40 Gew.%, stärker bevorzugt 10 Gew.% bis 35 Gew.% enthalten.In one embodiment, the coating material according to the invention comprises the organic binder or a mixture of several organic binders in an amount of 5% by weight to 50% by weight, based on the total solids content of the coating material. Preferably, the organic binder is contained in an amount of 7% by weight to 40% by weight, more preferably 10% by weight to 35% by weight.

Das photokatalytisch wirksame Mittel ist in einer Ausführungsform der Erfindung in einer Menge von 2 Gew.% bis 40 Gew.%, bezogen auf den Gesamtfeststoffgehalt des Beschichtungsmaterials, enthalten. Vorzugsweise ist des photokatalytisch wirksame Mittel in einer Menge von 3 Gew.% bis 30 Gew.%, stärker bevorzugt 5 Gew.% bis 25 Gew.%, noch stärker bevorzugt 5 Gew.% bis 10 Gew.% enthalten.The photocatalytically active agent is contained in an embodiment of the invention in an amount of from 2% by weight to 40% by weight, based on the total solids content of the coating material. Preferably, the photocatalytically active agent is contained in an amount of 3% by weight to 30% by weight, more preferably 5% by weight to 25% by weight, even more preferably 5% by weight to 10% by weight.

BaSO4 als funktioneller Füllstoff ist in einer Ausführungsform der Erfindung in einer Menge von 2 Gew.% bis 70 Gew.%, bezogen auf den Gesamtfeststoffgehalt des Beschichtungsmaterials, enthalten. Dabei ist der Gehalt an BaSO4 in der Beschichtungsmasse jedoch größer oder gleich dem Gehalt an photokatalytisch wirksamen Mittel. In einer bevorzugten Ausführungsform ist der funktionelle Füllstoff BaSO4 in einer Menge von 3 Gew.% bis 60 Gew.%, vorzugsweise 5 Gew.% bis 50 Gew.%, stärker bevorzugt 5 Gew.% bis 40 Gew.% enthalten. Die im erfindungsgemäßen Beschichtungsmaterial enthaltenen Füllstoffe können vollständig aus BaSO4 haltigem funktionellen Füllstoff wie vorstehend definiert bestehen. In einer anderen Ausführungsform werden zusätzlich auch herkömmliche Füllstoffe, die kein BaSO4 enthalten, verwendet. In diesem Fall sind die hier genannten Obergrenzen des Gehalts an funktionellem Füllstoff vorzugsweise auch als Obergrenzen für den Gesamtfüllstoffgehalt zu verstehen, d.h. der funktionelle Füllstoff enthaltend BaSO4 wird zu einem gewissen Teil mit herkömmlichem Füllstoff ersetzt.BaSO 4 as a functional filler is contained in an embodiment of the invention in an amount of from 2% by weight to 70% by weight, based on the total solids content of the coating material. However, the content of BaSO 4 in the coating composition is greater than or equal to the content of photocatalytically active agent. In a preferred embodiment, the functional filler is BaSO 4 in an amount of from 3 wt% to 60 wt%, preferably 5 wt% to 50 wt%, more preferably 5 wt% to 40 wt%. The fillers contained in the coating material of the invention may consist entirely of BaSO 4 -containing functional filler as defined above. In another embodiment, conventional fillers which do not contain BaSO 4 are additionally used. In this case, the upper limits of the functional filler content mentioned herein are preferably also to be understood as upper limits for the total filler content, ie the functional filler containing BaSO 4 is to a certain extent replaced by conventional filler.

In anwendungsfähiger Form vor dem Auftragen auf einen Beschichtungsgegenstand liegen die festen Bestandteile des Beschichtungsmaterials üblicherweise dispergiert in einem flüssigen Medium, z.B. Wasser vor. Typischerweise enthält das erfindungsgemäße Beschichtungsmaterial vor der Anwendung 10 Gew.% bis 50 Gew.% Wasser.When applied to a coated article prior to application, the solid components of the coating material are usually dispersed in a liquid medium, e.g. Water in front. Typically, the coating material according to the invention contains 10% by weight to 50% by weight of water before use.

Die Beschichtungsmasse der vorliegenden Erfindung kann neben den vorstehend genannten wesentlichen Bestandteilen (organisches Bindemittel, photokatalytisch wirksames Mittel und BaSO4) optional weitere übliche Additive enthalten, welchen einem Fachmann jeweils bekannt sind. Zu diesen Additiven zählen Netz- und Dispergiermittel, Verdicker, Entschäumer, Filmbildehilfsmittel, etc.The coating composition of the present invention may optionally contain, in addition to the above-mentioned essential ingredients (organic binder, photocatalytic agent and BaSO 4 ), further conventional additives, which are each known to a person skilled in the art. These additives include wetting and dispersing agents, thickeners, defoamers, film-forming aids, etc.

Gemäß der vorliegenden Erfindung ist der Gehalt an BaSO4 als funktionellem Füllstoff in der Beschichtungsmasse größer oder gleich dem Gehalt an photokatalytisch wirksamen Mittel. In einer stärker bevorzugten Ausführungsform beträgt das Gewichtsverhältnis von BaSO4 zu photokatalytisch wirksamen Mittel von 1:1 bis 10:1, vorzugsweise 1,2:1 bis 5:1.According to the present invention, the content of BaSO 4 as a functional filler in the coating composition is greater than or equal to the content of the photocatalytically active agent. In a more preferred embodiment, the weight ratio of BaSO 4 to photocatalytically active agent is from 1: 1 to 10: 1, preferably 1.2: 1 to 5: 1.

Das Beschichtungsmaterial der vorliegenden Erfindung kann in verschiedenen Anwendungsformen eingesetzt werden. Beispielsweise kann das Beschichtungsmaterial als eine Anstrichfarbe, insbesondere eine Fassadenfarbe, ein Lack, eine Lasur, eine Versiegelung, ein Schutzanstrich, eine Korrosionsschutzfarbe oder ein Putz vorliegen. Das Beschichtungsmaterial der vorliegenden Erfindung eignet sich insbesondere zum Einsatz im Außenbereich, z.B. zum Streichen, Bemalen, Verputzen oder Beschichten von Gebäudeteilen, wie etwa Betonwänden, Ziegelwänden oder anderen Wänden, Gemäuern, usw.The coating material of the present invention can be used in various applications. For example, the coating material may be present as a paint, in particular a facade paint, a paint, a glaze, a seal, a protective paint, a corrosion protection paint or a plaster. The coating material of the present invention is particularly suitable for use outdoors, for example, for painting, painting, plastering or coating of building parts, such as concrete walls, brick walls or other walls, masonry, etc.

Die vorliegende Erfindung betrifft auch die Verwendung eines erfindungsgemäßen Beschichtungsmaterials zum Abbau von in Atmosphärenluft enthaltenen Schadgasen, insbesondere volatilen organischen Verbindungen oder Stickoxiden, wie etwas NO oder NO2. Mit einer Beschichtungszusammensetzung der Erfindung ist es nun möglich, eine kostenoptimierte Beschichtungszusammensetzung bereit zu stellen, die unter natürlichen Umweltbedingungen hinsichtlich des Abbaus von z.B. Stickoxiden vorzugsweise einer Kinetik Erster Ordnung unterliegt. Unter natürlichen Umweltbedingen ist gemeint die

  • Konzentration an Stickoxiden NOx (NO und NO2) (liegt in der Regel unter 100 µg/m3 Jahresmittel)
  • Lichtintensität bzw. UV-A-Strahlung (liegt in der Regel zwischen 5 und 15 W/m2 im Jahresmittel bezogen auf die Tagstunden)
  • Rel. Luftfeuchte (liegt in der Regel zwischen 40 und 80%, Jahresmittel)
The present invention also relates to the use of a coating material according to the invention for degrading noxious gases contained in atmospheric air, in particular volatile organic compounds or nitrogen oxides, such as NO or NO 2 . With a coating composition of the invention, it is now possible to provide a cost-optimized coating composition which, under natural environmental conditions, preferably undergoes first-order kinetics in terms of degradation of, for example, nitrogen oxides. Under natural environmental conditions is meant the
  • Concentration of nitrogen oxides NO x (NO and NO 2 ) (usually less than 100 μg / m 3 annual mean)
  • Light intensity or UV-A radiation (usually between 5 and 15 W / m 2 annual mean in relation to the day hours)
  • Relative humidity (usually between 40 and 80%, annual average)

In einer bevorzugten Ausführungsform wird dabei das Beschichtungsmaterial der vorliegenden Erfindung im Außenbereich verwendet.In a preferred embodiment, the coating material of the present invention is used outdoors.

Die vorliegende Erfindung betrifft auch die Verwendung von BaSO4 als funktionellem Füllstoff wie vorstehend definiert zur Steigerung der Aktivität bzw. Effizienz eines photokatalytisch wirksamen Mittels in einem Beschichtungsmaterial, insbesondere hinsichtlich des Abbaus von in Umgebungsluft enthaltenen Schadgasen.The present invention also relates to the use of BaSO 4 as a functional filler as defined above for increasing the activity or efficiency of a photocatalytically active agent in a coating material, in particular with regard to the decomposition of noxious gases contained in ambient air.

Die vorliegende Erfindung wird im Folgenden unter Bezug auf spezielle Arbeitsbeispiele detaillierter beschrieben. Die angeführten Arbeitsbeispiele dienen lediglich der Illustration. Andere spezielle Ausführungsformen werden für den Fachmann auf Basis der vorliegenden Offenbarung offensichtlich sein.The present invention will be described in more detail below with reference to specific working examples. The working examples given are for illustration only. Other specific embodiments will be apparent to those skilled in the art based on the present disclosure.

BeispieleExamples Bestimmung der photokatalytischen AktivitätDetermination of the photocatalytic activity

Die photokatalytische Aktivität wurde in einem Closed-loop-Verfahren mit simultaner FTIR-Reaktionsverfolgung bestimmt. Der schematische Aufbau der verwendeten Messapparatur ist in Figur 1 gezeigt. Die Apparatur ist ein geschlossener Kreislauf, der aus folgenden Komponenten besteht:

  • Reaktor (R) aus Edelstahl (Grundfläche 0,2 m x 1 m) mit einer Glasabdeckung. In den Reaktor werden die Probenkörper (Beschichtungsaufzüge auf inertem Untergrund) eingelegt.
  • Leuchtkörper, Belichtungsapparatur (L)
  • FTIR-Spektrometer mit Langweggasmesszelle (IR)
  • regulierbare Pumpe (P) zur Zirkulation
  • hochdichte Edelstahl-Verbindungsschläuche (nicht in Figur 1 gezeigt)
Photocatalytic activity was determined in a closed-loop method with simultaneous FTIR reaction tracking. The schematic structure of the measuring apparatus used is shown in FIG. The apparatus is a closed circuit consisting of the following components:
  • Stainless steel reactor (R) (base area 0.2 mx 1 m) with a glass cover. In the reactor, the specimens (coating lifts on inert ground) are inserted.
  • Illuminant, exposure apparatus (L)
  • FTIR spectrometer with long-distance gas measuring cell (IR)
  • adjustable pump (P) for circulation
  • high-density stainless steel connecting hoses (not shown in FIG. 1)

Die Einbringung der Schadstoffe erfolgt über ein Septum (S). Als Schadgas wurde Methanol verwendet. Methanol ist im Vergleich zu anderen Schadgasen relativ stabil. Daher ist eine gesteigerte Abbaurate von Methanol auch aussagekräftig für andere, weniger stabile Schadgase. Das Gesamtvolumen des Systems beträgt 9,51.The introduction of pollutants via a septum (S). Methanol was used as noxious gas. Methanol is relatively stable compared to other noxious gases. Therefore, an increased rate of degradation of methanol is also meaningful for other, less stable noxious gases. The total volume of the system is 9.51.

Zur Messung wird die Luft im geschlossenen Kreislauf im Kreis umgewälzt. Das FTIR-Spektrometer als Detektor nimmt nach Zugabe des Schadstoffs in gegebenen Zeitabständen komplette Spektren vom Bereich 4000 cm-1 bis 700 cm-1 auf. Aus diesen Momentaufnahmen der Zusammensetzung der Atmosphäre im System kann kontinuierlich und ohne Zeitverzögerung die Konzentration des Schadstoffs in der Gasphase bestimmt werden.
Die Belichtung erfolgt mit UV-Leuchtröhren vom Typ Philips TL 40W/05, wenn die photokatalytische Aktivität im UV-Bereich bestimmt werden soll, oder herkömmliche "Haushaltsneonröhren" vom Typ Philips Master TL-D Super 80 36W/840, wenn die photokatalytische Aktivität im sichtbaren Bereich des Lichtes bestimmt werden soll. Die genauen Intensitäten sind bei den folgenden Ausführungsbeispielen und Vergleichsbeispielen angegeben.For measurement, the air is circulated in a closed circuit in a circle. The FTIR spectrometer as detector absorbs complete spectra ranging from 4000 cm -1 to 700 cm -1 at given time intervals after addition of the pollutant. From these snapshots of the composition of the atmosphere in the system can be determined continuously and without delay, the concentration of the pollutant in the gas phase.
Exposure is achieved with Philips TL 40W / 05 UV fluorescent tubes if UV photocurrent activity is to be determined, or Philips Master TL-D Super 80 36W / 840 conventional "Neonatal" tubes if the photocatalytic activity in the visible range of the light is to be determined. The exact intensities are given in the following embodiments and comparative examples.

Vergleichsbeispiel 1: Silikonharz-Fassadenfarbe ohne BaSOComparative Example 1: Silicone resin facade paint without BaSO 44

29,9 Gew.%29.9% by weight Wasserwater 8,2 Gew.%8.2% by weight Silikonharz (Feststoffgehalt: 50 Gew.%)Silicone resin (solids content: 50% by weight) 11,0 Gew.%11.0% by weight Styrol-Acrylat Bindemittel (Feststoffgehalt: 50 Gew.%)Styrene-acrylate binder (solids content: 50% by weight) 10,0 Gew.%10.0% by weight photokatalytisches, C-modifiziertes TiO2 (Kronos)photocatalytic, C-modified TiO 2 (Kronos) 10,0 Gew.%10.0% by weight Weißpigment TiO2 White pigment TiO 2 26,9 Gew.%26.9% by weight Silikatische FüllstoffeSilicate fillers 4,0 Gew.%4.0% by weight übliche Additive (Netz- u. Dispergiermittel, Verdicker, Entschäumer, Filmbildehilfsmittel, etc.)customary additives (wetting agents and dispersants, thickeners, defoamers, film-forming auxiliaries, etc.)

Ausführungsbeispiel 1: Silikonharz-Fassadenfarbe mit BaSOEmbodiment 1: Silicone resin facade paint with BaSO 44

29,9 Gew.%29.9% by weight Wasserwater 8,2 Gew.%8.2% by weight Silikonharz (Feststoffgehalt: 50 Gew.%)Silicone resin (solids content: 50% by weight) 11,0 Gew.%11.0% by weight Styrol-Acrylat Bindemittel (Feststoffgehalt: 50 Gew.%)Styrene-acrylate binder (solids content: 50% by weight) 10,0 Gew.%10.0% by weight photokatalytisches, C-modifiziertes TiO2 (Kronos)photocatalytic, C-modified TiO 2 (Kronos) 10,0 Gew.%10.0% by weight BaSO4 BaSO 4 26,9 Gew.%26.9% by weight Silikatische FüllstoffeSilicate fillers 4,0 Gew.%4.0% by weight übliche Additive (Netz- u. Dispergiermittel, Verdicker, Entschäumer, Filmbildehilfsmittel, etc.)customary additives (wetting agents and dispersants, thickeners, defoamers, film-forming auxiliaries, etc.)

Die Formulierungen gemäß Vergleichsbeispiel 1 und Ausführungsbeispiel 1 können durch Vermischen der genannten Komponenten in den angegebenen Mengen auf an sich bekannte Weise hergestellt werden. Die Formulierung aus Vergleichsbeispiel 1 und die Formulierung aus Ausführungsbeispiel 1 wurden jeweils auf Aluminiumfolie aufgetragen und unter normalen Raumbedingungen getrocknet. Vor der Bestimmung der photokatalytischen Aktivität wurden die Proben 120 Stunden lang vorbelichtet mit einer Intensität von 10 W/m2 UV-A. Die Proben wurden dabei noch alle 24 Stunden mit destilliertem Wasser befeuchtet und abgespült.The formulations according to Comparative Example 1 and Working Example 1 can be prepared by mixing the stated components in the stated amounts in a manner known per se. The formulation of Comparative Example 1 and the formulation of Example 1 were each applied to aluminum foil and dried under normal room conditions. Before determining the photocatalytic activity, the samples were pre-exposed for 120 hours with an intensity of 10 W / m 2 UV-A. The samples were still moistened every 24 hours with distilled water and rinsed.

Im Falle von Vergleichsbeispiel 1 und Ausführungsbeispiel 1 erfolgte die Belichtung mit sichtbarem Licht mit einer Gesamtintensität von 36,8 W/m2 im Wellenlängenbereich von 300 nm bis 800 nm. Der UV-A-Anteil (315 nm-380 nm) betrug 0,7 W/m2.In the case of Comparative Example 1 and Example 1, the exposure to visible light with a total intensity of 36.8 W / m 2 in the wavelength range of 300 nm to 800 nm took place. The UV-A fraction (315 nm-380 nm) was 0, 7 W / m 2 .

Die photokatalytische Abbaurate in Vergleichsbeispiel 1 betrug 1,4 mg m-2 h-1. Dagegen lag die photokatalytische Abbaurate in Ausführungsbeispiel 1 bei 3,1 mg m-2 h-1. Die Aktivitätssteigerung ist deutlich zu erkennen. Genauer gesagt wird durch das Ersetzen von Weißpigment TiO2 mit BaSO4 die photokatalytischen Aktivität mehr als verdoppelt.The photocatalytic degradation rate in Comparative Example 1 was 1.4 mg m -2 h -1 . In contrast, the photocatalytic degradation rate in Example 1 was 3.1 mg m -2 h -1 . The increase in activity is clearly visible. More specifically, by replacing white pigment TiO 2 with BaSO 4, the photocatalytic activity more than doubles.

Vergleichsbeispiel 2: 2K-Polyurethan-Farbe ohne BaSOComparative Example 2: 2K polyurethane paint without BaSO 44 Komponente A:Component A:

33,0 Gew.%33.0% by weight Wasserwater 32,0 Gew.%32.0% by weight vernetzbares Polyacrylat (Feststoffgehalt: 50 Gew.%)crosslinkable polyacrylate (solids content: 50% by weight) 12,0 Gew.%12.0% by weight photokatalytisches TiO2 (Sachtleben)photocatalytic TiO 2 (Sachtleben) 8,0 Gew.%8.0% by weight Weißpigment TiO2 White pigment TiO 2 12,0 Gew.%12.0% by weight CaCO3 CaCO 3 3,0 Gew.%3.0% by weight übliche Additive (Netz- u. Dispergiermittel, Verdicker, Entschäumer, etc.)customary additives (wetting and dispersing agents, thickeners, defoamers, etc.)

Komponente B:Component B:

100 Gew.% Härter: aliphatisches Polyisocyanat auf Basis von Hexamethylendiisocyanat HDI100% by weight hardener: aliphatic polyisocyanate based on hexamethylene diisocyanate HDI

Komponenten A und B werden vor der Anwendung im Verhältnis 100 : 12 gemischt.Components A and B are mixed in the ratio 100: 12 before use.

Ausführungsbeispiel 2: 2K-Polyurethan - Farbe mit BaSOEmbodiment 2: 2K polyurethane paint with BaSO 44 Komponente A:Component A:

33,0 Gew.%33.0% by weight Wasserwater 32,0 Gew.%32.0% by weight vernetzbares Polyacrylat (Feststoffgehalt: 50 Gew.%)crosslinkable polyacrylate (solids content: 50% by weight) 12,0 Gew.%12.0% by weight photokatalytisches TiO2 (Sachtleben)photocatalytic TiO 2 (Sachtleben) 8,0 Gew.%8.0% by weight Weißpigment TiO2 White pigment TiO 2 12,0 Gew.%12.0% by weight BaSO4 BaSO 4 3,0 Gew.%3.0% by weight übliche Additive (Netz- u. Dispergiermittel, Verdicker, Entschäumer, etc.)customary additives (wetting and dispersing agents, thickeners, defoamers, etc.)

Komponente B:Component B:

100 Gew.% Härter: aliphatisches Polyisocyanat auf Basis Hexamethylendiisocyanat HDI100% by weight hardener: aliphatic polyisocyanate based on hexamethylene diisocyanate HDI

Komponenten A und B werden vor der Anwendung im Verhältnis 100 : 12 gemischt.Components A and B are mixed in the ratio 100: 12 before use.

Die Komponente A aus Vergleichsbeispiel 2 und Ausführungsbeispiel 2 kann jeweils durch Vermischen der genannten Komponenten in den angegebenen Mengen auf an sich bekannte Weise hergestellt werden. Die Komponente B wird jeweils vor der Anwendung im angegebenen Mischungsverhältnis zugemischt. Die Formulierung aus Vergleichsbeispiel 2 und die Formulierung aus Ausführungsbeispiel 2 wurden jeweils auf Aluminiumfolie aufgetragen und unter normalen Raumbedingungen getrocknet. Vor der Bestimmung der photokatalytischen Aktivität wurden die Proben 120 Stunden lang vorbelichtet mit einer Intensität von 10 W/m2 UV-A. Die Proben wurden dabei noch alle 24 Stunden mit destilliertem Wasser befeuchtet und abgespült.Component A of Comparative Example 2 and Exemplary Embodiment 2 can each be prepared by mixing the stated components in the stated amounts in a manner known per se. Component B is mixed before each application in the specified mixing ratio. The formulation of Comparative Example 2 and the formulation of Example 2 were each applied to aluminum foil and dried under normal room conditions. Before determining the photocatalytic activity, the samples were pre-exposed for 120 hours with an intensity of 10 W / m 2 UV-A. The samples were still moistened every 24 hours with distilled water and rinsed.

In Vergleichsbeispiel 2 und Ausführungsbeispiel 2 erfolgte die Belichtung mit UV-Strahlung mit einer Gesamtintensität von 17,0 W/m2 im Wellenlängenbereich von 300 nm bis 800 nm. Der UV-A-Anteil (315nm-380nm) betrug 6,7 W/m2.In Comparative Example 2 and Exemplary Embodiment 2, the exposure was carried out with UV radiation with a total intensity of 17.0 W / m 2 in the wavelength range from 300 nm to 800 nm. The UV-A content (315 nm-380 nm) was 6.7 W / m 2 .

Die photokatalytische Abbaurate in Vergleichsbeispiel 2 betrug 16,2 mg m-2h-1. Die photokatalytische Abbaurate in Ausführungsbeispiel 2 betrug im Gegensatz dazu 20,3 mg m-2 h-1. Eine Aktivitätssteigerung ist deutlich zu erkennen. Ausführungsbeispiel 2 unterscheidet sich von Vergleichsbeispiel 2 lediglich dahingehend, dass der Füllstoff CaCO3 mit dem Füllstoff BaSO4 ersetzt wurde.The photocatalytic degradation rate in Comparative Example 2 was 16.2 mg m -2 h -1 . The photocatalytic degradation rate in Example 2 was in contrast 20.3 mg m -2 h -1 . An increase in activity is clearly visible. Embodiment 2 differs of Comparative Example 2 only in that the filler CaCO 3 was replaced with the filler BaSO 4 .

Ausführungsbeispiel 3: Silikonharz-Putz mit BaSOEmbodiment 3: Silicone resin plaster with BaSO 44

11,5 Gew.%11.5% by weight Wasserwater 2,5 Gew.%2.5% by weight Silikonharz (Feststoffgehalt: 50 Gew.%)Silicone resin (solids content: 50% by weight) 5,5 Gew.%5.5% by weight Styrol-Acrylat Bindemittel (Feststoffgehalt: 50 Gew.%)Styrene-acrylate binder (solids content: 50% by weight) 6,5 Gew.%6.5% by weight Ethylen-Vinylester-Terpolymer Bindemittel (Feststoffgehalt: 50 Gew.%)Ethylene-vinyl ester terpolymer binder (solids content: 50% by weight) 5,0 Gew.%5.0% by weight photokatalytisches TiO2 photocatalytic TiO 2 24,0 Gew.%24.0% by weight BaSO4 BaSO 4 2,0 Gew.%2.0% by weight Aluminiumhydroxidaluminum hydroxide 3,0 Gew.%3.0% by weight übliche Additive (Netz- u. Dispergiermittel, Verdicker, Entschäumer, Filmbildehilfsmittel, etc.)customary additives (wetting agents and dispersants, thickeners, defoamers, film-forming auxiliaries, etc.) 40,0 Gew.%40.0% by weight Struktursandsand structure

Die Formulierung gemäß Ausführungsbeispiel 3 kann durch Vermischen der genannten Komponenten in den angegebenen Mengen auf an sich bekannte Weise hergestellt werden. Der Putz wurde auf Aluminiumfolie aufgetragen und unter normalen Raumbedingungen getrocknet. Vor der Bestimmung der photokatalytischen Aktivität wurde die Probe 120 Stunden lang vorbelichtet mit einer Intensität von 10 W/m2 UV-A. Die Probe wurde dabei noch alle 24 Stunden mit destilliertem Wasser befeuchtet und abgespült.The formulation according to embodiment 3 can be prepared by mixing the said components in the stated amounts in a manner known per se. The plaster was applied to aluminum foil and dried under normal room conditions. Before determining the photocatalytic activity, the sample was pre-exposed for 120 hours with an intensity of 10 W / m 2 UV-A. The sample was moistened every 24 hours with distilled water and rinsed.

Bei diesem Beispiel erfolgte die Belichtung mit UV-Strahlung mit einer Gesamtintensität von 17,0 W/m2 im Wellenlängenbereich von 300 nm bis 800 nm. Der UV-A-Anteil (315 nm - 380 nm) betrug 6,7 W/m2.In this example, the exposure was carried out with UV radiation with a total intensity of 17.0 W / m 2 in the wavelength range of 300 nm to 800 nm. The UV-A content (315 nm - 380 nm) was 6.7 W / m 2 .

Die photokatalytische Abbaurate betrug 6,1 mg m-2 h-1. Dies ist insbesondere im Hinblick auf den relativ geringen Photokatalysator-Gehalt eine bemerkenswerte Aktivität.The photocatalytic degradation rate was 6.1 mg m -2 h -1 . This is a remarkable activity particularly in view of the relatively low photocatalyst content.

Claims (12)

  1. A coating material comprising
    (a) at least one organic binding agent,
    (b) at least one photocatalytically active agent, and
    (c) BaSO4 as functional filler, wherein the content of BaSO4 in the coating compound is greater than or equal to the content of photocatalytically active agent.
  2. The coating material according to Claim 1, wherein the coating material is largely free, preferably free, from siliceous binding agents.
  3. The coating material according to Claim 1 or 2, wherein the functional filler comprises BaSO4, which is present as natural barium sulphate, as synthetic barium sulphate, or as lactic acid filler, containing more than 60 % by weight, preferably more than 80 % by weight, of BaSO4.
  4. The coating material according to Claim 3, wherein the mixed filler containing BaSO4 has a water solubility of less than 0.1 g/l at 20 °C.
  5. The coating material according to one of the preceding claims, wherein the organic binding agent is selected from polymer dispersions, redispersing agents, polymers or mixed polymers, is preferably selected from epoxy resins, alkyd resins, acryl resins, melamine/formaldehyde resins, silicone resins, silanes, polysiloxanes, polyacrylates, polymethacrylates, polyvinyl compounds, polyurethanes, polyethers or polyesters and copolymers of mixtures thereof, and is more preferably selected from polymer dispersions, containing acrylates, styrene acrylates, vinyl acetates, vinyl chlorides and mixed polymers and copolymers thereof.
  6. The coating material according to one of the preceding claims, wherein the photocatalytically active agent is selected from a photocatalytically active metal oxide or metal sulphide, preferably metal oxide, of Ti, Zn, Fe, Mn, Mo and/or W, preferably with a proportion of at least 60 % by weight, particularly preferably at least 80 % by weight, in particular at least 90 % by weight, based on the total quantity of the photocatalytically active agent, and wherein the photocatalytically active agent is preferably selected from zinc sulphide, zinc oxide, titanium oxide and mixtures thereof.
  7. The coating material according to claim 6, wherein the photocatalytically active material consists of titanium dioxide, in particular in amorphous and/or partly crystalline form, rutile or anatase form, hydrates of titanium oxides, and mixed forms thereof, which are preferably doped with C, N and/or S.
  8. The coating material according to one of the preceding claims, wherein the organic binding agent is contained in a quantity of 10 % by weight to 35 % by weight, preferably 15 % by weight to 30 % by weight, and/or
    the photocatalytically active agent is contained in a quantity from 1 % by weight to 15 % by weight, preferably 3 % by weight to 13 % by weight, more preferably 5 % by weight to 10 % by weight, even more preferably 5 % by weight to 7 % by weight,
    and/or
    BaSO4 is contained as functional filler in a quantity from 1 % by weight to 70 % by weight, preferably 3 % by weight to 60 % by weight, more preferably 5 % by weight to 50 % by weight, even more preferably 5 % by weight to 40 % by weight, in each case based on the total solid content of the coating material,
    and wherein the content of BaSO4 in the coating is greater than or equal to the content of photocatalytically active agent, wherein the ratio by weight of BaSO4 to photocatalytically active agent is from 1:1 to 5:1, preferably 1.2:1 to 5:1.
  9. The coating material according to one of Claims 1 to 8, wherein the coating material is a paint, in particular house paint, a lacquer, a glaze, a sealant, a protective coating, an anti-corrosion paint or a plaster, in particular for use outdoors.
  10. Use of BaSO4 as a functional filler for increasing the activity of a photocatalytically active agent in a coating material, wherein the coating material comprises
    (a) at least one organic binding agent,
    (b) at least one photocatalytically active agent, and
    (c) BaSO4 as functional filler.
  11. The use according to Claim 10 for degrading harmful gases contained in atmospheric air, in particular volatile organic compounds (VOCs) or nitrogen oxides, such as NO or NO2.
  12. The use according to Claim 11, wherein the coating material is used outdoors.
EP12007180.8A 2012-10-17 2012-10-17 Photocatalytic coatings with fillers Active EP2722370B1 (en)

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CN104449140A (en) * 2014-12-04 2015-03-25 浙江汇千高飞新材料有限公司 Catalyst coating and preparation method thereof
CN108300207A (en) * 2017-08-09 2018-07-20 安徽红桥金属制造有限公司 With high coloring and weatherability electrification box paint vehicle and preparation method thereof
EP3505247A1 (en) 2017-11-30 2019-07-03 STO SE & Co. KGaA Photocatalytic coatings with sulphidic semiconductors
CN112246246A (en) * 2020-09-30 2021-01-22 常州烯奇新材料有限公司 Visible light response photocatalyst composite material and preparation method thereof

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ATE269958T1 (en) 1997-04-23 2004-07-15 Cadexair APPARATUS AND METHOD FOR REMOVAL AND IN SITU BIODEGRADATION OF FATS FROM A KITCHEN FAN
DE19757496A1 (en) 1997-12-23 1999-06-24 Studiengesellschaft Kohle Mbh Photocatalysts comprising metal oxide and metal ions
JP2002146293A (en) * 2000-11-16 2002-05-22 Dainippon Toryo Co Ltd Aqueous emulsion coating material
JP2002226709A (en) * 2001-01-29 2002-08-14 Sekisui Chem Co Ltd Photocationically polymerizable composition
DE20306431U1 (en) 2003-04-25 2004-09-02 Maxit Deutschland Gmbh Cement-free composition useful for producing photocatalytically active coatings comprises a photocatalyst and calcium sulfate
DE102004018338A1 (en) 2004-04-15 2005-11-10 Sto Ag coating material
ATE417902T1 (en) 2004-06-04 2009-01-15 Sto Ag COATING COMPOSITION
DE102004054048A1 (en) * 2004-11-05 2006-05-11 Basf Ag coating materials
ES2357083T3 (en) * 2007-08-28 2011-04-18 Basf Se TIO2 PHOTOACTIVE IN COATING MATERIALS.
US20090163656A1 (en) * 2007-12-21 2009-06-25 Envont Llc Hybrid vehicle systems
WO2010029596A1 (en) * 2008-09-10 2010-03-18 株式会社ピアレックス・テクノロジーズ Coating composition and method for forming sealant layer with coating film

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